Maturation of brain structure underpins its functionality. From birth, brain structure and neurobehavior abilities progressively mature. However, specific link between these two entities remains unclear. This study therefore aims to investigate such correlation between neonatal neurobehavior and brain white matter (WM) microstructural development measured by diffusion tensor imaging (DTI)-fractional anisotropy (FA). Results indicated that neonatal behavior abilities significantly correlated with sensorimotor WM FAs; while active-tone just correlated with motor-associated WM. These findings demonstrate the specialized correlations of specific neurobehavior abilities with microstructural maturation in corresponding WMs, suggesting the potential role of DTI in assessing the neonatal neurodevelopment in clinical practice.